Viscose spinning solution



Patented Apr. 22, 1952 viscose, SPINNING SOLUTION Robert D. MacLaurinand William 0. Israel, Lakewood, Ohio, assignors to Industrial RayonCorporation, Cleveland, Ohio,

Delaware a corporation oit No Drawing Application July 16, 1948,

' 7 Serial No. 39,194

l The present invention has for its object a new and improved viscosesolution for use in the production of such yarn as well as a process bywhich such viscose solutions and produced.

In the preparation of viscose spinning solutions the viscose iscustomarily filtered one or more times through various fine cloth mediabefore it is extruded into a coagulating bath. Difficulty however isfrequently encountered in producing viscose solutions that are free ofminute undispersed and undissolved particles which clog the pores of thefilter media prematurely or pass through the pores and later clog theorifices of spinnerets thereby resulting in yarns of low strength andpoor uniformity. Such extraneous particles may consist of resinousmaterials found in wood pulp undissolved or partially dissolvedcellulose xanthate gels and semisolids, etc. The presence of suchparticles in a filtered viscose solution is usually evidenced by thelack of transparency and high turbidity of the spinning solution. Insome situations even relatively large sized particles in the form offluid semisolids or gel-like substances successively slip throughjthepores of the filter media. In addition such particles upon standing in astored and filtered viscose solution may tend to agglomerateand as aresult further increase the difficulties mentioned.

In order to eliminate one or more of the difficulties mentioned therehave been proposed heretofore the incorporation of various organicsurface-active compounds at one or more of the stages of-viscoseproduction. In general however such additives have not been entirelysuccessful for one or more of the following reasons, i. e., they may beunstable in the caustic soda solutions encountered in the various stagesof viscose prepartion; they may tend to lose their dispersing power inviscose on standing during the normal viscose storage and ripeningperiods; their dispersing powers may be too low, thus requiring yarn maybe the incorporation of excessive amounts which may patible with andreduce the efiicienc'y of th. in-

crustationj inhibiting agent employed in a co- 1 agulating bath.

In accordance with the present invention it has been found that theabove mentioned difficulties may be obviated and that an improvedviscose spinning solution inay be produced by incorporat- 13 Claims.(Cl. 106165) ing into the viscose at any stage of its preparation aproduct formed from the reaction of at least about 12 moles of analkylene oxide with one mole of a primary or secondary aliphatic amineor mixtures thereof, the amines being alkyl or alkenyl amines containingfrom 6 to 18 carbon atoms.

Among the alkylene oxides which are particularly suitable in forming theamine-alkylene oxide reaction products employed in the present inventionare ethylene and propylene oxide. Advantageous results are derived wherethe aminealkylene oxide compounds employed represent the reaction ofbetween about 12 and 100 moles of an alkylene oxide per mole amine andwith particular advantage where the moles of alkylene oxide per mole ofamine are between about 14 and 75 and preferably between about 18 and60. a

The above defined primary or secondary amines or mixtures thereof whichare reacted with an alkylene oxide may if desired contain othersubstitutents in addition to the alkyl and alkenyl radicals specifiedsuch as, for example, aryl radicals or other amine radicals. In thelatter situation there may be mentioned the mono-, di-, trietc. amines.Examples of various typical amines which may be reacted to produce theamine derivatives employed in the present invention will appear later inthe specification:

In general the amine reactants having alkyl or alkenyl radicalscontaining more than 6 carbon atoms are preferred such as for exampleoxide compounds made from mixtures of amines having a mean molecularweight of at least about 175 or 185 and more advantageouslyof at leastabout 200. With similar advantage mixtures of amines may be used asstarting materials in which at least about mole percent of the amineshave radicalscontaining from 12 to 18 carbon atoms and in additionthereto either 20 mole percent containing from 14 to 18 carbon atoms orthe amine mixture having a mean molecular weight of about 175.Particularly advantageous results are derived where 80 mole percent ofthe amine mixtures have radicals containing '14 to 18 carbon atoms or inaddition 20 molepercent containing from 16 to 18 carbon atoms.

Similar advantages are derived where the amine mixture has a meanmolecular weight of at least 185 and mole percent thereof have Inpracticing the present invention the amine:

alkylene oxide reaction product may be added if desired at one or moreof the viscose preparation stages such as, for example, (a) to achemically prepared wood pulp which has been refined for the manufactureof viscose, prior to or during the shredding of the alkali cellulose,(c)

to cellulose xanthate crumbs before or during the 4 the stages of theviscose preparation so as to form a viscose spinning solution containingfor example between about 0.01 and 0.2%, by weight, of the reactionproduct based on the weight of the viscose. w

' The following specific examples in which parts by weight are givenwill serve to illustrate the present invention, although it will beunderstood that the invention is not limited to the specific conditionsset forth.

Example 1 534 parts of normal primary octadecenylamine is mixed with 5parts of a 50% aqueous sodium dissolving step, and (d) to dissolvedcellulose xanthate (viscose) before or after filtration or both.Particularly advantageous results are derived where the reaction productis added to and admixed with a viscose solution prior to filtration.

The compounds useful in practicing the invention may, in general, beprepared in the following manner. A weighed quantity of one or more ofthe amines mentioned is mixed with a small amount of an alkalinecatalyst such as, for example, about 0.5 to 2%, by weight, sodiumhydroxide in the form of a solid or of a 50% aqueous solution. Otheralkali or alkaline earth metal catalysts may be used in the place ofsodium hydroxide, such as for example, potassium hydroxide or the alkalimetal alcoholates, e. g. sodium methylate. The mixture is introducedinto a pressure resistant vessel such as an autoclave which is equippedwith suitable agitating, heating and cooling means. The contents of theautoclave are then heated while stirring to an initial reactiontemperature of from about 100 C. to about 200 C., the range betweenabout 125 C. to about 150 C. being preferred to facilitate the controlof the reaction. After the initial reaction temperature is attained aweighed amount of an alkaline oxide such as, for example, ethylene orpropylene oxide is then introduced into the autoclave preferably througha suitable meter while the mixture is agitated. The rate of addition ofthe alkylene oxide depends among other things upon the efficiency of themeans for dissipating the heat of the reaction. The duration of thereaction may extend over a period of from 1 to 3 hours or more dependingamong other things upon the amount and character of each of thereactants. 'I'he'temperature during the reaction is preferablymaintained at about 125 C. and the pressure is not permitted to exceedabout 200 pounds per square inch. After all of the alkylene oxide hasbeen introduced the temperature control and agitation of the contents ofthe autoclave is continued until the reaction is complete as isindicated by a gradual drop in pressure and by a rapid decrease intemperature. The contents of the autoclave may then be discharged andpermitted to cool to room temperature. The reaction products are allsoluble in water or alcohol and also in various aqueous acid oralkalineliquids.

Depending upon the character and molecular weight of the amine ormixture of amines and upon the number of moles of alkylene oxide whichare reacted the character of the reaction product may range from aviscous liquid to a semisolid or solid. In practicing the presentinvention a quantity of the amine-alkylene oxide reaction product whichis dissolved in a suitable solvent such .as for example Water is addedto andmixed with viscose forming materials at one or more of hydroxidesolution as a catalyst and placed in an autoclave where it is heated toan initial reaction temperature of C. while stirring the mixture. Then1056 parts of ethylene oxide is gradually introduced into the autoclaveover a period of one hour and forty minutes and the temperature ispermitted to rise to about 144 C. while the maximum pressure attained isabout 100 pounds per square inch. After all of the ethylene oxide hasbeen introduced and the reaction is completed as is indicated by agradual decrease in pressure to zero gauge, the material is evacuatedfrom the autoclave and permitted to cool to room temperature. Thereaction product thus formed is a brownish waxy solid which is solublein water and represents the reaction of about 12 moles of ethylene oxideper mole of amine.

A suitable quantity of the reaction product is dissolved in water tomake up a 30%, by weight, stock solution and the stock solutiongradually added to and mixed With a filtered viscose spinning solutionuntil the viscose contains, about 0.05%, by weight, of the reactionproduct based on the weight of the viscose, the viscose containing about8% cellulose and about 6.5% sodium hydroxide. The viscose spinningsolution prepared in' this manner is clear and transparent, and whenextruded into a coagulating bath containing, by weight, about 10%sulfuric acid, 20% sodium sulfate and 1% zinc sulfate, does not clog thespinneret orifices after prolonged continuous periods of spinning. Inaddition the presence of the amine reactionproduct in the viscose and inthe coagulating bath inhibits the formation of 'incrustations on thespinneret face and on other devices operatively associated with thecoagulating bath liquid. The yarn produced is desirably uniform inappearance and strength.

Example 2 The procedure of Example 1 is followed with the exception that2112 parts of ethylene oxide is introduced into the autoclave over aperiod of about 2 /2 hours. The reaction product representing thereaction of about 24 moles of ethylene oxide per mole of amine issimilar to the product of "Example 1 both in'character and inits'eifectiveness with the exception that only about 0.025%, by weight,of the product is incorporated in the viscose.

Example 3 The procedure of Example 1 is followed with the exception-that 267. parts of the octadecenylamine is reacted with 1180 parts ofpropylene oxide, the latter being introduced over a period of 3 to 4hours. The initial reaction temperature is about C. and the temperatureis not permitted to rise above about C. while the .pressure is notpermitted to rise above about 85 pounds per square inch. Th reactionproduct is similar in character and effectiveness to that of Example 1and represents the reaction of about 20 moles of propylene oxide permole of the amine.

Example 4 5 parts of a 50% sodium hydroxide solution is mixed with 71parts of secondary dodecyl amine and 215 parts of normal primaryoctadecyl amine and the mixture placed in an autoclave where it isheated to an initial reaction temperature of 130 C. while stirring themixture. Then 1320 parts of ethylene oxide is gradually introduced intothe autoclave over a period of about 2 hours andthe temperature ispermitted to rise toabout 150 C. while the maximum pressure attained isabout 150- pounds per square inch; After all of the ethylene oxide hasbeen introduced and the reaction is completed as is indicated by agradual decrease in pressure to zero gauge, the material is evacuatedfrom the autoclave and permitted to cool to room, temperature. Thereaction produce formed is a brown waxy solid which is soluble in waterand represents the reaction of about 30 moles of ethylene oxide permean'mole of the mixture of amines having a mean molecular weight ofabout 286. An aqueous solution of the resulting reaction product isprepared and incorporated in a viscose solution in the manner and underthe conditions of Example 1 with the I Example 5 5 parts of a 50%aqueous sodium hydroxide solution as a catalyst is mixed with thefollowing normal primary amines; 133 parts of octadecadienyl amine; 48parts of hexadecyl' amine, 21 parts of tetradecyl amine, and, 37 partsof. dodecyl amine. The mixture is then placed in an autoclave where itis heated to an initial reaction temperature of about 130 C. whilestirring the mixture. Then 1760 parts of ethylene oxide is graduallyintroduced into the autoclave'over a period of about 2 /2 hours and thetemperature is permitted to rise to about 160 C. while the maximumpressure attained is about 150 pounds per square inch. After all of theethylene oxide has been introduced and the reaction is completed asindicated by a gradual decrease in pressure to zero gauge, the materialis evacuated from the autoclave and permitted to. cool to roomtemperature. The reaction product formed is a waxy solid. which issolublein. Water and represents thereaction of about 40 moles. ofethylene oxide per mean mole of the mixture of amines having a, mean.molecular Weight. of about. 240. The resulting reaction. product isdissolved in water to form an aqueous solution containing about 30%, byweight, of the product and. this. solution is gradually added to andmixed with a freshly prepared viscose solution prior to the filtrationthereof. The composition of the viscose is the same as that described inExample 1. A sufllcient quantity of the reaction product is added toform a viscose solution containing about 0.05%, by weight, of theproduct based on the weight of the viscose. The viscose solutionprepared. in this manner results in longer periods of continuous viscosefiltration and also in a filtered viscose spinning solution which isclear, trans-,

parent. The yarn produced is desirably uniform and has improvedstrength.

Example 6.

5 parts of a 50% aqueous sodium hydroxide solution as a catalyst ismixed with the following normal primary amines; 5 parts of hexyl amine,6 parts of octylamine, 16 parts decylamine, 83 parts of dodecylamine, 43parts of tetradecylamine and 40 parts of octadecylamine. The mixture isthen reacted with 2200 parts of ethylene oxide in the manner and underthe conditions described in Example 5. The reac-- tion productrepresents the reaction of about 50 moles of ethylene oxide with onemean mole of the mixture of amines having a mean molecular weight ofabout19l.

A quantity of the reaction product is dissolved in water to form a 30%,by weight, aqueous stock solution and the stock solution is graduallyadded to and mixed with a viscose solution of the composition describedin Example 1. The addition is made both before filtration and afterfiltration of the viscose in quantities sufiicient to form a filteredviscose spinning: solution containing about 0.04%, by weight, of thereaction product.

Example 7 The procedure of Example 5 is followed with the exception that2640 parts of ethylene oxide is introduced into the autoclave over aperiod of about 3% hours and reacted with the following normal primaryamines; 8 parts of decylamine, 28 parts of dodeoylamine, 85 parts oftetradecylamine, 72 parts of hexadecylamine and 27 parts ofoctadecenylamine'. The product represents the reaction of about'60 molesof ethylene oxide with one mean mole of the mixture of amines having amean molecular weight of about 220.

Example 8 The procedure in this example is the same as that set forth inExample 7 with the exception that 3520 parts of ethylene oxide isintroduced into the autoclave over a period of about 4 /2 hours toproduce a reaction product having about moles of ethylene oxide per meanmole of th mixture of amines.

Example 9 The procedure of Example 5 is followed with the exception thatthe following mixture of primary normal amines are reacted; 24 parts ofhexadecylamine, 27 parts of octadecylamine, 80 parts ofoctadecenylamine, and 133 parts of octadecadienyl amine. The resultingreaction product which is incorporated in the viscose represents thereaction of about 40 moles of ethylene oxide per mean mole, the aminemixture having a mean molecular weight of about 264.

Example 10 A suitable quantity of the amine-ethylene oxide reactionproduct of Example 9 was dissolved in water to form a 50%, by weight,aqueous solution and the aqueous solution sprayed onto a batch. ofalkali cellulose (soda cellulose) prior to the shredding operation. Thequantity of the reaction product employed is sufficient to form ashreddedv alkali cellulose containing about 0.8%, by weight, of thereaction product based on the weight'of the cellulose. By preparingviscose in this-manner a finer and more uniformly shredded alkalicellulose is obtained which in turn permits a more uniform and morecomplete xanthation of the alkali cellulose and dissolution of thecellulose xanthate into viscose. In addition more rapid, and moreprolonged periods of continuous viscose filtration are achieved and aclear and transparent viscose results which may be spun into yarn ofdesirable uniformity and strength.

Example 11 The procedure of Example is followed with the exception thatthe aqueous solution of the amine-ethylene oxide reaction product isgradually introduced into a cellulose xanthate dissolving vessel andmixed with the cellulose xanthate crumbs and the aqueous caustic sodasolvent therefor, prior to the completion of the dissolv ing step. Asufiicient quantity of the reaction product is employed to form aviscose containing about 0.08%, by weight, of the reaction product. Theresults obtained are similar to those of Example 10 as regards thefiltration of the viscose, the uniformity and clarity of the filteredviscose, and character of the yarn product.

Example 12 treated wood pulp containing about 0.2%, by.

weight, of the reaction product based on the weight of the bone drycellulose. tered viscose solution prepared from the above treated woodpulp is then added a suflicient quantity of the 50% aqueous solution ofthe amine derivative to form a viscose containing about 0.05%, byweight, of the amine derivative based on the weight of the viscose. Theresults obtained are similar to those described in Example 10.

In practicing the present invention tlie'amine-' alkylene oxide reactionproduct may, if desired, be employed in the preparation of various typesof viscose solutions; such as'for example those containing and those notcontaining delustering materials such as for example finely divided anddispersed particles of titanium dioxide, waxes, oils, etc. Under certainconditions the incorporation of the amine-alkylene oxide reactionproduct may with advantage improve the degree, stability, and uniformityof the dispersion of the delustering particles in the viscose.

As previously stated the amine derivatives may be added to andincorporated in chemically prepared cellulose such as wood pulp,'cotton,etc. prior to the formation of alkali cellulose therefrom, or, ifdesired, they may be addedto' the alkali cellulose. In either situationit is found advantageous to incorporate between about 0.01 and 1.0%, byweight, of the amine derivatives, based on the weight of the bone drycellulose and with particular advantage" between about 0.05 and 0.8%.

Further advantages are however derived where relatively small amounts ofthe amine derivatives are added both at some point before the xanthationstep and also after the dissolution of the cellulose xanthate intoviscose. Advantageously the amounts added at the several stages ofviscose preparation may be such as to form a viscose solution containingbetween about 0.01 and 0.2%, by weight, of the amine derivative based onthe weight of the viscose solution.

Other amines which may be reacted with an alkylene oxide to produce theproducts useful in the present invention may include normal monoaminesof the aliphatic series such as hexylamine, heptylamine, octylamine,nonylamine,

To an unfila 8 decylamine, undecylamine, dodecylamine, tridecylamine,tetradecylamine, pentadecylamine,

hexadecylamine, heptadecylamine, octadecylamine; or, diamines or thealiphatic series including 1,6 hexanediamine, 1,7 heptane diamine, 1,8octyl diamine, 1,9 nonyl diamine, 1,10 dodecylamine, 1,11 undecyldiamine, 1,12 dodecyl diamine, l,13 tridecyl diamine, 1,14 tetradecyldiamine, 1,15 pentadecyl diamine, 1,16 hexadecyl diamine, 1,17heptadecyl diamine, 1,18 octadecyle diamine, or normal monoaminesderived from the olefinic series such as hexenyl amine, heptenyl amine,octenyl amine, nonenyl amine, decenyl amine, undecenyl amine, dodecenylamine, tridecenyl amine, pentadecenyl amine, hexadecenyl amine,heptadecenyl amine, and octadecenyl amine, or diamines derived from theolefinic series such as 1,6 amino hexene, 1,7 amino heptene, 1,8 amino,octene, 1,9 amino nonene, 1,10 aminodecene, 1,11 amino undecene, 1,12amino dodecene, 1,13 amino tridecene, 1,14 amino tetradecene, 1,15 aminopentadecene, 1,16 amino hexadecene, 1,17 amino heptadecene, and 1,18amino octadecene.

We claim:

1. A viscose spinning solution having incorporated therein between about0.01 and 0.2%, by weight, of a product formed by the reaction of atleast about 12 moles of an alkylene oxide with one mean mole of amixture of primary aliphatic amines selected from the group consistingof alkyl and alkenyl amines containing from 6 to 18 carbon atoms; atleast about mole percent of said mixture of amines containing from 12 to18 carbon atoms.

2. A viscose spinning solution having incorporated therein between about0.01 and 0.2%, by weight, of a product formed from the reaction ofbetween about 12 and moles of an alkylene oxide with one mean mole of amixture of primary aliphatic amines selected from the group consistingof alkyl and alkenyl amines containing from 6 to 18 carbon atoms, atleast about 80 mole percent of said mixture of amines containing from 6to 18 carbon atoms, at least about 80 mole percent of said mixture ofamines containing from 14 to 18 carbon atoms. 7

3. A viscose spinning solution having incorporated therein between about0.01 and 0.2%, by weight, of a product formed from the reaction ofbetween about 12 and 100 moles of an alkylene oxide with one mean moleof a mixture of primary aliphatic amines selected from the groupconsisting of alkyl and alkenyl amines containing from 6 to 18 carbonatoms; at least about 80 mole percent of said mixture of aminescontaining from 14 to 18 carbon atoms and at least about 20 mole percentcontaining from 16 to 18 carbon atoms.

,4. A viscose spinning solution having incorporated therein betweenabout 0.01 and 0.2%, by weight, of a product formed from the reaction ofbetween about 14 and 75 moles of an ethylene oxide with one mean mole ofa mixture of primary aliphatic amines selected from the groupconsisting' of alkyl and alkenyl amines containing from 6 to 18 carbonatoms, said mixture of amines having a mean molecular weight of at leastabout 200 and atleast about 70 mole percent of said mixture of aminescontaining from 16 to 18 carbon atoms.

5. A viscose spinning solution according to claim 11 in which ethyleneoxide is used as the alkylene oxide reactant.

6.- A viscose spinning solution according to claim 1 in which ethyleneoxide is used as the alkylene oxide reactant.

7. A viscose spinnin solution according to claim 1 in which propyleneoxide is used asthe alkylene oxide reactant.

8. A viscose spinning solution having incorpo-;' rated therein betweenabout 0.01 and 0.2%; by weight, of a product formed from the reactionof;between about 12 and 100 moles of ethylene ox" e" with one mole ofnormal primary octadecylamifie.

9. A viscose spinning solution having incorporated therein between about0.01 and 0.2%, by weight, of a product formed from the reaction ofbetween about 12 and 100 moles of ethylene oxide with one mole of normalprimary octa decenylamine. f

10. A viscose spinning solution having incorpoi rated therein betweenabout 0.01 and 0.2%, by weight, of a product formed from the reaction ofbetween about 12 and 100 moles of ethylene oxide sisting of alkyl andalkenyl amines containing.

from 6 to 18 carbon atoms.

12. A viscose spinning solution having incorpo 30 rated therein betweenabout 0.01 and 0.2%,.by-

weight, of a composition comprising a product formed by the reaction ofbetween about 12' and 100 moles of an alkylene oxide with one mole of a10 primary aliphatic amine selected from the group consisting of alkyland alkenyl amines containing from 12 to 18 carbons atoms.

13. A viscose spinning solution having incorporated therein betweenabout 0.01 and 0.2%, by weight, of a product formed from the reaction ofbetween about 12 and 100 moles of an alkylene oxide with one mean moleof a mixture of primary aliphatic amines selected from the groupconsisting of alkyl and alkenyl amines containing from 6 to 18 carbonatoms; said mixture of amines having a mean molecular weight of at leastabout 185.

ROBERT D. MACLAURIN. WILLIAM O. ISRAEL.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS- Number Name Date 2,226,119 De Groote Dec. 24,1940 2,310,207 Bley Feb. 9, 1943 2,362,217 Schlosser et a1 Nov. 7, 19442,440,094 Israel Apr. 20, 1948 2,442,331 Cresswell June 1, 1948 FOREIGNPATENTS Number Country Date 358,114 Great Britain Oct. 5, 1931 789,522France Oct. 30, 1935 665,359 Germany Sept. 23, 1938

1. A VISCOSE SPINNING SOLUTION HAVING INCORPORATED THEREIN BETWEEN ABOUT0.01 AND 0.2%, BY WEIGHT, OF A PRODUCT FORMED BY THE REACTION OF ATLEAST ABOUT 12 MOLES OF AN ALKYLENE OXIDE WITH ONE MEAN MOLE OF AMIXTURE OF PRIMARY ALIPHATIC AMINES SELECTED FROM THE GROUP CONSISTINGOF ALKYL AND ALKENYL AMINES CONTAINING FROM 6 TO 18 CARBON ATOMS; ATLEAST ABOUT 80 MOLE PERCENT OF SAID MIXTURE OF AMINES CONTAINING FROM 12TO 18 CARBON ATOMS.